Process for the dyeing of materials consisting of anion-modified polyacrylonitrile, polyamide and polyester fibres

ABSTRACT

Compositions and a process for dyeing and printing synthetic materials of polyacrylonitrile, polyamides, or polyesters which contain anionic groups which comprises using a treating composition for aforesaid materials which consists of an aqueous dispersion of a basic dyestuff salt and a polynuclear aromatic sulfonic acid whereby the fixing times are reduced and fast and level dyeings are produced.

United States Patent 11 1 Hildebrand et al.

[111 3,900,283 [4 1 Aug. 19, 1975 [75] Inventors: Dietrich Hildebrand, Odenthal;

Winfried Kruckenberg; Werner Kuhnel, both of Leverkusen; Hans Heinz Molls, Cologne-Flittard; Karlheinz Wolf, Cologne-Stammheim, all of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen-Bayerwerk, Germany [22] Filed: Sept. 9, 1969 [21] Appl. No.: 856,468

[30] Foreign Application Priority Data Mar. 1, 1969 Germany 1910587 [52] U.S. Cl. 8/21 A; 8/21 B; 8/2] C; 8/173; 8/168 [51] Int. Cl D06p 5/00 [58] Field of Search 8/178, 179,177, 21, 173, 8/21 A, 21 B, 21 C, 168 A [56] References Cited UNITED STATES PATENTS 1,613,228 l/l927 H07. 8/173 2,893,816 7/1959 Tsang et al..... 8/177 AB 2,955,009 10/1960 Pitts 8/177 AB 3,288,551 11/1966 Raff 8/21 3,504,997 4/1970 Clapham et a1 8/21 A FOREIGN PATENTS OR APPLICATIONS 823,345 11/1959 United Kingdom 8/177 867,006 5/1961 United Kingdom 8/177 933,483 8/1963 United Kingdom 8/177 1,222,056 4/1965 Germany 8/177 549,179 7/1956 Belgium 8/177 OTHER PUBLICATIONS Chem. Abstract, July 10, 1967, Co]. 10063. Zollinger, Amer. Dyestuff Rep., March 7, 1960, pages 142, 143, 144& 149.

Schmidlin, Preparation and Dyeing of Synthetic Fibres, Pub. April 1, 1963, pages 176-180, pub. by Chapman & Hall Ltd., London, Eng.

D. Trotman, Dyeing and Chemical Technology of Textile Fibres, 3rd Edition, Oct. 1963, pp. 329-330, pub. by Griffin, London, Eng.

Hoffman, German Auslegesc'hrift 1,260,074, 2/1/68, 2 pages spec. No drawing.

Douglas, American Dyestuff Reporter, Feb. 1 l, 1951, pages Pl22-P125, TP89OA512.

Innarone, American Dyestuff Reporter, Feb. 14, 1966, pages 52-55, TP89OA512.

Leddy, American Dyestuff Reporter, pp. 57, 58, 65-68, 4/18/60, TP890A512.

Egli, Textil Veredlung, Vol. 2, No. 1 1, pages 856-864, pub 1967.

Primary ExaminerDonald Levy Attorney, Agent, or Firm-Plumley & Tyner [57] ABSTRACT Compositions and a process for dyeing and printing synthetic materials of polyacrylonitrile, polyamides, or polyesters which contain anionic groups which comprises using a treating composition for aforesaid materials which consists of an aqueous dispersion of a basic dyestuff salt and a polynuclear aromatic sulfonic acid whereby the fixing times are reduced and fast and level dyeings are produced.

7 Claims, No [Drawings PROCESS FOR THE DYEING OF MATERIALS CONSXSTING OF ANION-MODIFIED POLYACRYLONITRILE, POLYAMIDE AND POLYESTER FIBRES The subject-matter of the invention is a process for the dyeing or printing, especially the continuous dyeing or printing, of synthetic fibre materials of polyacrylonitrile, polyamides or polyesters which contain anionic groups, or of mixtures thereof with other fibre materials. The process is characterised by the use of aqueous dispersions of sparingly water-soluble salts obtained from basic dyestuffs which are free from carboxylic acid and sulphonic acid groups with polynuclear aromatic sulphonic acids.

The term synthetic fibre materials containing anionic groups refersto those materials which can be dyed with basic dyestuffs and contain anionic groups such as sulphonic acid, carboxylic acid, sulphimide or phosphonic acid groups. Suitable fibre materials are in particular, filaments, fabrics or knitted fabrics consisting of polyacrylonitrile or of copolymers of acrylonitrile with other vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl alcohol, acrylic and methacrylic acid esters and amides, such as are described, for example, in British Patent Nos. 823,345; 867,006; 902,074; 933,483 and in German Patent Nos. 1,222,056 and 1,260,074, or those consisting of acid-modified aromatic polyesters, for example, poly-condensation products obtained from terephthalic acid, sulphoterephthalic acid and ethylene glycol (type Dacron 64 of E. l. Dupont de Nemours Co.), such as are described, for example, in Belgian Patent Specification No. 549,179 and US. Pat. No.

2,893,816, i.e. polyethylene glycol terephthalates con taining sulphonic acid groups. Suitable fibre materials are, furthermore, those consisting of copolyether esters obtained from p-hydroxybenzoic acid, terephthalic acid and ethylene glycol, which are modified by carboxylic and/or sulphonic acid groups. Suitable fibre materials of polyamides are, for example, polyhexanemethylene-diamine adipate, polycaprolactam and poly-m-amino-undecanic acid, modified by sulphonic acid groups.

Fibre mixtures which can be dyed or printed according to the process of the invention are, for example, those consisting of the above fibre materials which contain anionic groups, and of cotton, regenerated cellulose, wool and polyester fibres which contain no anionic groups, for example, those of terephthalic acid and l,4-bis-hydroxymethyl-cyclohexane or ethylene glycol, and of non-acid-modified polyamide fibres, for example those of poly-caprolactam or polyamides obtained from hexamethylene-diamine and adipic acid.

The fibre material to be dyed may be a double or treble mixture, for example, in the form of mixed fabrics or mixed knitted fabrics consisting of the fibre material which contains anionic groups and of one or two of the aforesaid fibre materials which contain no anionic groups; the mixing ratio may vary within wide limits. Fibre mixtures which contain about 45 70 percent of fibre materials with anionic groups are especially suitable, for example. I

Salts of basic dyestuffs which are suitablefor' the process according to the invention are the salts of basic dyestuffs which are free from carboxylic acid'and sulphonic acid groups, with polynuclear aromatic mono-,

di-, trior tetrasulphonic acids, especially those of the naphthalene series; the di-, triand tetrasulphonic acids should be specially mentioned because their salts are readily precipitated with the basic dyestuff, the ratio anion/cation in the salt is advantageous, and the nonfixed dyestuff particles are more easily washed out.

The following compounds are mentioned by way of example: naphthalenel sulphonic acid, naphthalene-2- sulphonic acid, naphthalene-disulphonic acid-( 1,4), naphthalene-disulphonic( l ,5), naphthalenedisulphonic acid-(1,6), naphthalene-disulphonic acid- (2,5), naphthalene-disulphonic acid-(2,6), naphthalene-disulphonic acid-( 2,7), naphthalene-trisulphonic acid-(1,3,5), naphthalene-trisulphonic acid-( 1,3,6) or naphthalene-trisulphonic acid-( 1 ,3 ,7), naphthalene-tetrasulphonic acid-( 1 ,3 ,5 ,7 and pyrene-tetrasulphonic acid-( 1 ,3,6,8).

The salts of the basic dyestufis to be used according to the invention are prepared by reacting water-soluble basic dyestuff salts with the aforesaid organic sulphonic acids or their water-soluble salts, such as the sodium salts, in an aqueous medium; the sparingly watersoluble salts are thus precipitated and can be separated in the usual way.

Suitable water-soluble basic dyestuff salts are, for example, dyestuff bases which are quaternised on at least one aliphatically or cyclically bound nitrogen atom,for example, those of the azo, anthraquinone, phthalocyanine, methine, hydrazone, azacyanine, styryl, acridine or nitro series, as well as the carbonium salts of the diand triphenylmethane series, the oxonium salts of the oxazine series or the sulphonium salts of the thiazine series.

The sparingly soluble dyestuff salts so obtained are formulated in the usual way, ie brought into the form suitable for application from an aqueous dispersion.

This conversion is carried out according to known processes, preferably by grinding with non-ionic and/or anionic dispersing agents.

Examples of non-ionic dispersing agents are the ethylene oxide products of fatty amines, fatty acids, fatty alcohols with a chain of about 12 20 carbon atoms; furthermore, ethylene oxide addition products of alkylphenols the alkyl chain of which contains 8 12 carbon atoms; as well as the ethylene oxide addition products of alkylarylor arylphenols with 7 50 mols ethylene oxide.

Examples of anionic dispersing agents are sodium alkylaryl sulphonates such as the sodium salts of di-nbutylnaphthalenel -sulphonic acid, diisobutylnaphthalene-sulphonic acid, dinaphthylmethane-disulphonic acid; reaction products of cresol, 2-naphthol-sulphonic acid-(6) and formaldehyde; as well as products of sulphite waste liquor.

The proportion of dispersing agents to dyestuff salt depends on the dispersibility of the dyestuff salt and may vary within wide limits. The following proportions have proved particularly suitable: parts of dyestuff salt 2 20 parts of non-ionic dispersing agent and/or 2 20 parts of anionic dispersing agent.

Concentrated aqueous preparations can be obtained from the dyestuff salts thus formulated by suitable mechanical comminution (colloidal mil], subsequently stirrer ball mill with grinding elements of glass with a diameter of 0.3 0.8 mm).

The subject-matter of the invention also comprises concentrated aqueous preparations of sparingly watersoluble salts obtained from basic dyestuffs which are free from carboxylic acid and sulphonic acid groups, with polynuclear aromatic sulphonic acids, said preparations containing about l5 50 percent by weight of dyestuff salt, about 0.3 percent by weight of a nonionic dispersing agent, and about 0.3 5 percent by weight of an anionic dispersing agent.

In detail, the process according to the invention is carried out by padding the fibre materials on a foulard or printing them with aqueous dispersions of the sparingly soluble dyestuff salts to be used according to the invention and subsequently subjecting them, usually after an intermediate drying, to a heat treatment by means of hot air, contact heat or steam (thermosolisation) temperatures of about 180 to 230C being applied.

The dyebaths are prepared from the sparingly soluble dyestuff salts in the usual way by stirring the dyestuff salts formulated as described above in water, optionally at an elevated temperature and optionally with the use of thickening agents, for example, those based on sodium alginate, cellulose ethers or polyacryloamide. In general, the quantity of thickening agent amounts to about 5 20 parts per 1000 parts of dyebath. The dyebath may moreover contain small amounts of organic or inorganic acids, such as formic acid or acetic acid, as well as sodium bisulphite or sodium dihydrogen phosphate. However, the pH value of the bath should not be below 4.

The dyestuff salts to be used according to the invention can also be applied together with anionic dyestuffs, such as acid, direct and reactive dyestuffs or non-ionic dyestuffs for dyeing mixed fabrics, for example, for the single-bath dyeing of mixed fabrics consisting of polyacrylonitrile or polyester fibres which contain anionic groups and of wool or cellulose fibres. When reactive dyestuffs are used, compounds of alkaline reaction, such as sodium bicarbonate or disodium hydrogen phosphate, may be added to the dyebaths. It is expedient to add sodium m-nitrobenzene sulphonate and butyrolactam to the baths in order to avoid overboiling.

If the sparingly soluble basic dyestuff salts and anionic dyestuffs are used simultaneously for the singlebath dyeing of mixed fabrics, fixation of the anionic dyestuffs on the fibre materials concerned is carried out previously or simultaneously, likewise by a thermal tion and without intermediate rinsing, applying and fixing the anionic or non-ionic dyestuff in a second bath.

The basic dyestuff salts to be used according to the invention are generally applied in amounts of about 5 40 g/litre of dyebath. For the dyeing of mixed fabrics, it is recommended to adjust the amounts of acid, direct or reactive dyestuffs to be added to the proportion of the corresponding fibre component in the mixed fabric. For every part of basic dyestuff salt there should be used at the most l part of nonionic acid, direct or reactive dyestuff.

The acid which may be added usually amounts to about I 3O g/litre of dyebath. The quantities of alkaline compounds which may also be added, for example, sodium bicarbonate or disodium hydrogen carbonate, amount to about 1 l0 g/litre of dyebath.

With the aid of the process according to the invention it is possible to dye fibre materials containing anionic groups, and especially their mixtures with cellulose fibres, with short fixing times and, in particular, in a continuous process, with basic dyestuffs to obtain fast and level dyeings. A particular advantage of the process according to the invention over dyeing with watersoluble salts of basic dyestuffs consists in the improvement of the fixation yield and, when dyeing mixed fabrics, the improved reserve of the accompanying fibre component as well as the fact that the dyestuff particles which are not fixed and adhere to the accompanying fibre are more easily washed out. This is of particular importance when dyeing fibre mixtures of polyacrylonitrile and regenerated cellulose and must be considered as a precondition for producing continuous dyeings of equal laps on this material.

A further advantage of the process according to the invention is the improvement of the stability of the padding liquor during the single-bath dyeing with anionic dyestuffs, as well as an improvement of the fixation yield in the presence of anionic dyestuffs.

The parts given in the following Examples are parts by wieght. The dyestuff numbers refer to Colour Index, 2nd edition, Vol. Ill.

The terms polyacrylonitrile, polyamide and polyester materials refer to the corresponding anion-modified materials, unless otherwise stated.

EXAMPLE- 1 20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula treatment, or in a second step, after passage through a onsi ting of second bath, for example, an alkaline padding bath, by means of steam or of an alkaline shock bath. However, fixation can also be carried out by prolonged storage at room temperature or elevated temperature. After fixation, the material is rinsed and dried. However, the process can also be carried out by applying the sparingly soluble basic dyestuff salt in a first bath and, after fixa- 20 parts of the dyestuff salt 2 parts of the reaction product of 1 mol 0- hydroxydiphenyl with 14 mol ethylene oxide 1 part of the sodium salt of the condensation product of 2 mol naphthalene-Z-sulphonic acid with 1 mol formaldehyde and 44 parts of water are mixed with 50 parts of a conventional acrylamide thickening with hot air at 200C for 90 seconds. The fabric is then agent and i v padded on a foulard with an alkali solution consisting 930part s of warm water, and the resultant padding of 50 g/litre sodium bicarbonate and 200 g/litre sodium liquor is padded on a foulard with a liquor absorpsulphate, again with a liquor absorption of 100 percent, tion of 100 percent on to a polyacrylonitrile fabric. 5 and steamed at 102C for 90 seconds. The fabric is then The fabric is subsequently dried at 120C for 60 rinsed first cold with overflow and then with change of seconds and thermosolised on a stenter with hot air baths at 70 100C for 1 minute each time, and subseat 200C for 90 seconds. The fabric is then rinsed quently cold. A clear turquoise-blue dyeing is obtained.

first cold with overflow and then with change of baths at 70 100C. 10

A red dyeing of good fas tness properties is obtained.

If the dyestuff is used in the form of the water-soluble methosulphate, a weaker and duller dyeing is obtained.

If the basic dyestuff is used in the ionic water-soluble form, there is obtained a dyeing the staple fibre component of which is strongly soiled with basic dyestuff and very difficult to rinse clear, and which exhibits strongly unequal laps when dyed in a continuous operation.

EXAMPLE 2 Parts of a dispersion of the sparingly water-soluble EXAMPLE 3 dyestuff salt of the formula 20 Parts of a dispersion of the sparingly water-soluble H N-C 1:1

.0 L CH5 5 01 consisting of dyestuff salt of the formula N (i N N 2 5 0 on S 9 \s/ \C H --N L'- GHz 06 2 4 .2 0 S0 20 parts of the dyestuff salt consisting of 2 parts of the reaction product of nonylphenol with 30 parts of the dyestuff salt 20 mols ethylene oxide 2.4 parts of the condensation product of 1 mol meth- 2 parts sodium lignin sulphonate and ylstyryl-phenol with mols ethylene oxide and l 10 parts of water are mixed with 50 31.6 parts of water are mixed with 10 parts of the reactive dyestuff of the formula 50 parts of an acrylamide thickening agent and (so nmz s H 2 c1 0 hth 1 1 N C ll- 8. 00 an ne 9 y q I 01 so -NH -50 Na N parts urea 60 930 parts of warm water, 50 parts of an acrylamide thickening agent and and the resultant padding liquor is padded with a liquor 860 parts of warm water absorption of percent on to a mixed fabric consistand the resultant padding liquor is padded on a foulard ing of 60 parts polyacrylonitrile and 40 parts polynosic with a liquor absorptiton of 100 percent on to a mixed rayon. The fabric is dried at C f0r60 seconds and fabric consisting of 60 parts polyacrylonitrile and 40 5 thermosolised at 200C by means of hot air for 90 secparts of staple fibre. The material is subsequently dried onds. The fabric is then padded on a foulard with a dyeat 120C for 60 seconds and thermosolised on a stenter stuff solution consisting of 10 g/litre of the dyestuff of the formula I 2 01 Sc m so an c I s I N m J 6 mo s so iia and 20 g/litre sodium bicarbonate with a liquor absorption of .100 percent and, without drying, steamed at l02C for 90 seconds; it is subsequently rinsed as described in Example 1.

A clear red dyeing of good fastness properties is obtained. If the basic dyestuff is used in theionic watersoluble form, there is obtained a dull dyeing with a low yield; its shade changes with the washing conditions.

If the naphthalene-disulphonic acid-(2,5) is replaced with naphthalene-disulphonic acid 1,5)

naphthalene-disulphonic acid 1,6)

naphthalene-disulphonic acid -(2,6)

naphthalene-disulphonic acid -(2,7)

or naphthalene-disulphonic acid 1,4) then dyeings of the same good fastness properties are obtained.

EXAMPLE 4 20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula consisting of 30 parts of the dyestuff salt 3 parts of the reaction product of 1 mol oleyl alcohol with 25 mols ethylene oxide padded on a foulard with a liquor absorption of 100 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of staple fibre. The fabric is then dried at 120C for 90 seconds and steamed with saturated steam at 1 C for 120 seconds; subsequently it is dipped for 5 seconds into an alkali solution consisting of 200 parts sodium sulphate 50 parts sodium carbonate and 30 parts of a sodium hydroxide solution of density An intense blue dyeing of good fastness properties is obtained. if the basic dyestuff is used in the soluble form, there is obtained an unstable padding liquor and varying fixation results.

EXAMPLE 5 20 Parts of a dispersion of the sparingly water-soluble 1 parts of the reaction product of 2 mol Z-naphthol- 6-sulphonic acid with 1 mol formaldehyde/bisulphite and 67 parts of water are mixed with 20 parts of the dyestuff of the formula parts of an acrylamide thickening and 910 parts of warm water, and the resultant padding liquor is dyestuff salt of the formula 40 consisting of 20 parts of the dyestuff salt 2 parts of the reaction product of 1 mol phydroxydiphenyl with 1 mol benzyl chloride and 14 mol ethylene oxide 2 parts of the condensation product of 2 mol naphthalene-Z-sulphonic acid with 1 mol formaldehyde and 56 parts of water are mixed with 20 parts of the dyestuff of the formula SO NZL 9 10 and with 1 part of an alginate thickening agent and 50 parts of a polyacrylamide thickening agent and 828 parts of water with a liquor absorption of 80 per- 910 parts of war w ter, cent, rolled up and left to stand covered for 24 hours.

and the resultant padding liquor is padded on a foulard It is subsequently rinsed first with overflow and then with a liquor absorption of 100 percent on to a mixed 5 with change of baths at 60 80C.

fabric consisting of 60 parts polyacrylonitrile and 40 A clear red dyeing is obtained. If the basic dyestuff parts of staple fibre. The fabric is then dried at 120C is used in its ionic water-soluble form, an expensive infor 90 seconds and thermosolised at 200C by means of termediate rinsing is necessary before application of hot air 90 Seconds- The fabrie is Subsequently the direct dyestuff, because the rinsing clear of the dye- PP seconds ihto an alkali Solution which has ingwould otherwise encounter great difficulties.

been heated to 9 and consists of If the dyestuff salt is formed with the use of naphthal- 150 Parts sofhum Sulphate ene-trisulphone-( 1,3,7), instead of naphthalene- 50 Parts Sodlum and trisulphonic acid-( 1,3,6), an equally valuable dyeing is 30 parts of a sodium hydroxide solution of density obtained 1.356.

An intense yellow dyeing of good fastness properties EXAMPLE 7 is obtained. If the basic dyestuff is used in its watersoluble ionic form, there is obtained an unstable d- Parts of a dispersion of the sparingly water-soluble ding liquor with varying fixation results. 20 dyestuff salt of the formula I e CH=CH-N- Q -OGH EXAMPLE 6 consisting of 20 parts of the dyestuff salt 2 parts of the reaction product of 1 mol p- 10 Parts of a dispersion of the sparingly water-soluble hydroxydiphenyl with 1 mo benzyl chloride and 14 dyestuff salt of the formula mo] ethylene oxide 2 5 I CH 0 n- -ii=N- -n 5 2H4 \GHg ON o i ti f 2 parts of the condensation product of 2 mol naphthalene-sulphonic acid-( 1) with 1 mol formal- 30 parts of the dyestuff salt 50 dehyde and 3 parts of the reaction product of 1 mol p- 56 R f Water hydroxydiphenyl with 1 mol benzyl chloride and 14 are mixed with mol eth l id and 20 parts of the dyestuff of the formula and the resultant padding liquor is padded on a foulard N with a liquor absorption of 80 percent on to a mixed H fabric consisting of 60 parts polyacrylonitrile and parts of staple fibre; the fabric is subsequently dried at 67 parts of water are mixed with 01 F parts of an acrylamide thickening agent and N 940 parts of warm water, v Naogs N I 120C for seconds and thennosolised at 200C for New 3 seconds. The fabric is then padded on the foulard 5 with a dyestuff solution consisting of and 20 parts of the dyestuff 35,780 65 50 parts of an acrylamide thickening agent and 150 parts urea 910 parts of warm water, 1 part of a glycerol ether Sulphate and the resultant padding liquor is padded on a foulard with a liquor absorption of percent on to a mixed fabric consisting of 55. parts polyacrylonitrile and 45 parts of wool. The impregnated fabric is dried at 90C for 120 seconds and subsequently steamed at 102C for 12 minutes. If steaming is carried out with saturated steam at 102 110C, the steaming time can be reduced accordingly. After steaming, the fabric is soaped first cold with overflow, then with the use of an anion active detergent at 70 100C.

A clear orange dyeing is obtained.

If the basic dyestuff is used in its ionic dissolved form, staining precipitates occur in the padding bath and the dyeing obtained shows a strong soiling of the wool component.

EXAMPLE 8 15 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula 0,0Hs s e -c-- n. Q ii 8 1m:- 11/ \CH2CH3 5 fabric consisting of 55 parts polyacrylonitrile, 37 parts of staple fibre and 8 parts of cellulose fibres. The fabric is subsequently dried at 120C for 90 seconds and thermosolised at 180C with hot air for 90 seconds. The fabric is subsequently padded on a foulard with a dyestuff solution consisting of 10 parts of the dyestuff of the formula N SOCH HO NHJ 2 5 parts urea 10 parts sodium bicarbonate 3 parts of an alginate thickening agent and 957 parts of water with a liquor absorption of 80 percent and, without intermediate drying, steamed at 102C for 90 seconds. After steaming, the fabric is first rinsed cold with overflow and then soaped at 60 90C with change of baths and with the use of 2.5 parts of an anion-active detergent per 1000 parts of water. A clear red dyeing I O of good fastness properties is obtained. If the dyestuff O n is used in its soluble ionic form, a dull dyeing is ob- 2 CH -CH -O-GGH tained, which is difficult to wash out and the shade of which depends on the washing conditions. 0 N EXAMPLE 9 W 10 Parts of a dispersion of the sparingly water-soluble 0 dyestuff salt of the formula CH N CH 4 consisting of 30 parts of the dyestuff 25 parts of a sulphite waste liquor product 25 parts of a reaction product of cresol, 2-naphtholsulphonic acid and formaldehyde 40 parts of an acrylamide thickening agent and 940 parts of water. The resultant padding liquor is padded on a foulard with a liquor absorption of 80 percent on to a mixed consisting of fabric is then rinsed first cold with overflow, then at 70 sulphonate.

A clear yellow dyeing is obtained. If the basic dyestuff is used in its soluble ionic form, then there is obtained a dyeing which is difficult to wash out.

and EXAMPLE .1 l

1 part of a dispersion of the dyestuff No. 12,790 Parts of a dispersion of the sparingly water-soluble each consisting of dyestuff salt of the formula 2 5 S0 S0 -N=N -N CH5 15 parts of dyestuff and V ,l I consisting of 85 parts of the reaction product of cresol, 2-naphparts of the dyestuff salt thol-sulphonic acid-(6) and formaldehyde 2 parts of the reaction product of 1 mol 0- 50 parts of an acrylamide thickening agent and hydroxydiphenyl with 1-4 mol ethylene oxide 929 parts of warm water. 1 part of the sodium salt of the condensation product The resultant padding liquor is padded on a foulard of 2 mol naphthalene-Z-sulphonic acid with 1 mol with a liquor absorption of 80 percent on to a mixed formaldehyde and fabric consisting of 50 parts polyacrylonitrile and 50 44 art of water parts of unmodified polyester fibre. The fabric is then i are mixed with dried at 120C for 60 seconds and thermosolised at 5 rt f the dye tuff of the formula 200C for 90 seconds. It is subsequently soaped first cold, then at 70 100C with the use of nonionic or b 0 c I anion active detergents A clear lue dyeing is ob 5 N S 2 H tamed. t i HQ NH I If the basic dyestuff is used in its ionic water-soluble l form, then a substantially weaker. dyeing is obtained. N

EXAMPLE 10 40 CH 10 Parts of a dispersion of the sparingly water-soluble I dyestuff salt of the formula Naogs $0 119.

with naphthalene-Z-sulphonic acid consisting of 50 parts of anacrylamide thickening and 35 parts of the dyestuff salt 930 parts of water 3.5 parts of the reaction product of 1 mol methylstyand padded on a foulard wiflq a squeezing effect of 80 ryl-phenol and 50 mol ethylene oxide percent on to a mixed fabric consisting of parts of 2 parts sodium dinaphthyl-methane-disu1phonate and 60 anion-modified polyester and 30 parts of cotton. 59.5 parts of water are mixed with The fabric is then dried at 120C for 60 seconds and 12 parts of a sodium alginate thickening agent and thermosolised at 200C for 90 seconds. It is then pad- 978 parts of water ded on a foulard with a solution consisting of and the liquid is padded on a foulardrwith a liquor ab- 350 parts of calcined sodium carbonate sorption of percent on to a fabric of anion-modified 65 650 parts of water and polyester. The fabric is then dried at 120C for 60 sec- 30 parts of a sodium hydroxide solution of density onds and thermosolised at 200C for seconds. The 1.35 and steamed for 5 minutes. Rinsing and soaping is C, with the use of 2 g/litre sodium alkylcarried out as described in Example 1. A level red dyeing is obtained. If the red dyestuff is used in its soluble form, the resulting dyeing is only weak by comparison.

EXAMPLE l2 5 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula consisting of 30 parts of the dyestuff salt 2.4 parts of the condensation product of 1 mol methyl-styryl-phenol with 50 mol ethylene oxide 31.6 parts of water 10 parts of the dyestuff of the formula N Q m2 \sa c-Nl: s 011 -03 N 80 N8- H0 HN-C- N c1 Ila-0 S 50 119.

40 parts urea and 1 part sodium m-nitrobenzene-sulphonate are mixed with 12 parts of a sodium alginate thickening and 917 parts of water and the liquor is padded on the foulard with a liquor absorption of percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of cotton. The fabric is then dried at 120C for seconds and thermosolised at 200C for 90 seconds. The fabric is subsequently padded on a foulard with a solution containing 70 g/litre sodium bicarbonate and 200 g/litre sodium sulphate. It is steamed at 102C for 120 seconds, rinsed cold with overflow and subsequently soaped at 70 C with the use of 2 g/litre sodium paraffin- 50 sulphonate. A clear red dyeing is obtained. If the basic dyestufi' is used in its soluble form, then there is obtained a weaker dyeing the shade and colour strength of which depend on the washing conditions.

S0 Na NH sn/ mo s S0 Na SO CH:

40 parts urea 1 part sodium m-nitrobenzene-sulphonate are mixed with 12 parts of a sodium alginate thickening agent and 917 parts of water and padded on a foulard with a 1iquor absorption of 100 percent on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of staple fibre. The fabric is then dried at C for 60 seconds and steamed with pressurized steam at 1 15C for 2 minutes. The fabric is subsequently padded on a foulard with a solution con- I sisting of 350 parts of calcined sodium carbonate 30 parts of a sodium hydroxide solution of density 1.35 650 parts of water and, after an air passage of 60 seconds, allowed to stand at room temperature for 3 hours. The fabric is rinsed and soaped as described in Example 1. A clear red dyeing is obtained.

If the basic dyestuff is used in its ionic soluble form, precipitates are formed in the dyebath, which lead to blotchy dyeings.

55 EXAMPLE l3 EXAMPLE 14 20 Parts of a dispersion of the sparingly water-soluble 20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula dyestuff salt of the formula 9 H5 0 CH -CH -NCH S0 consisting of 20 parts of the dyestuff salt 2 parts of the reaction product of 1 mol 0- and padded on a foulard on to a mixed fabric consisting of 60 parts of anion-modified polyamide and parts of acid-modified polyamide. The fabric is subsequently dried at 120C for 90 seconds and then steamed with pressurized steam at 115C for 5 minutes. It is rinsed with water at 70C for 5 minutes. A clear bicolour dyeing is obtained.

EXAMPLE 15 20 Parts of a dispersion of the sparingly water-soluble dyestuff salt of the formula consisting of 20 parts of the dyestuff salt 2 parts of the reaction product of 1 mol phydroxydiphenyl with 14 mol ethylene oxide 1 part of the sodium salt of the condensation product of 2 mol naphthalene-2-su1phonic acid with 1 mol formaldehyde and 44 parts of water are mixed with 10 parts of the dyestuff of the formula xao s $0 M;

5 parts sodium bicarbonate parts urea 5 parts butyrolactam and 910 parts of water and padded on a foulard on to a mixed fabric consisting of 60 parts polyacrylonitrile and 40 parts of cotton. The fabric is dried at C for 2 minutes and then thermosolised at 200C for 90 seconds. The material is rinsed and soaped as described in Example 1. A level red dyeing is obtained.

If the basic dyestuff is used in the water-soluble ionic form, then a substantially weaker dyeing is obtained.

EXAMPLE 16 25 Parts of the dispersion of dyestuff salt described in Example 5, part 1 are stirred into 975 parts of a thickening agent consisting of 300 parts of a 10% starch ether thickening 300 parts of a 40% British gum thickening 20 parts of 30% acetic acid 20 parts thio-diethylene glycol 10 parts N,N-bis-(p-cyanoethyl)-formamide 5 parts citric acid i 345 partsof water 1000 parts of thickening agent This printing paste is applied to a fabric of polyester fibres and the dyestuff is fixed. by a thermosol process 30 (at C for 4 seconds); the fabric is subsequently rinsed and soaped. A yellow print is obtained which is substantially clearer and stronger than the print obtained when 'the dyestuff is used in its ionic Watersoluble form.

EXAMPLE 17 25 Parts of a 1:1 mixture of the dispersion of dyestufi salt described in Example 5, part 1, and the dyestuff dispersion described in Example 9 are stirred into 975 parts of the thickening agent described in Example 6.

The printing pastes so obtained are applied to a fabric of polyacrylonitrile fibres in the usual way by screen or rouleaux printing, and the dyestuffs are fixed by a thermosol process (190C for 40 seconds); the fabric is subsequently rinsed and soaped. An intense green print is obtained the yield of which is appreciably better as in the case where the dyestuffs are used in their ionic water-soluble form.

EXAMPLE 1 8 The printing pastes according to Example 17 are printed on to a polyester fabric and the dyestuff fixed by thermosolisation 190C for 40 seconds), the fabric is subsequently rinsed and soaped. The print obtained is appreciably clearer and deeper as in the case where the dyestuffs are used in their ionic water-soluble form.

EXAMPLE 19 35 Parts of the dyestuff dispersion described in Example l are stirred into 965 parts of the thickening agent described in Exam- 20 ple 16. The printing paste is applied to a fabric of polyacrylonitrile fibres and the dyestuff is fixed by steaming under 0.4 atm. excess pressure for 20 minutes; the fabric is EXAMPLE 21 1.2 Parts of an aqueous dispersion of the sparingly water-soluble dyestuff salt of the formula,

consisting of 20 parts of the dyestuff salt 2 parts of the reaction product of 1 mol 0- hydroxydiphenyl with .14 mol ethylene oxide 1 part of the sodium salt of the condensation product of 2 mol naphthalene-2-sulphonic acid with 1 mol formaldehyde and 44 parts of water subsequentlyv rinsed and soaped. A level and smooth 25 are mixed w print is obtained, whereas the print obtained with the use of the dyestuff in its ionic water-soluble form is uneven and blotchy.

' EXAMPLE 20 Preparation of the dyestuff salts 75 Parts of the dyestuff of the formula are dissolved in 750 parts of water at 70C. A solution of 100 parts of the sodium salt of naphthalene-lsulphonic acid in '1000 parts of water, likewise at 70C, is added thereto with good stirring within 15 minutes until precipitation no longer occurs. Stirring is continued for one-half hour and the mixture is then cooled to 20C. The precipitated red dyestuff salt is filtered off with suction, washed with water until free from electrolyte, and dried. Yield: 100 parts of the dyestuff salt of the formula All the sparingly soluble basic dyestuff salts to be used according to the invention can be obtained in an analogous manner with the use of the corresponding cHN(cH) water-soluble basic dyestuff salts and the corresponding aromatic sulphonic acids or their salts.

parts of water at 50C and combined with a solution of 0.8 parts of the dyestuff No. 35,780

50 parts of anhydrous sodium sulphate 1 part of the reaction product of 1 mol oleyl alcohol with 50 mol ethylene oxide 2 parts of a polyphosphate giving a pH value of 4.8

6 CH ObO is rinsed, first only with an overflow of cold water, subsequently with a hot solution of 2 parts sodium alkyl sulphonate in 988 parts of water. i

A clear blue-red mixed dyeing is obtained; if the basic dyestuff is used in the non-formulated form, the staple fibre is appreciably more soiled.

21 2.2 EXAMPLE 22 said materials with other fiber materials, wherein the 1 Part of a dispersion of the sparingly water-soluble internal anionic groups are strong anionic groups that dyestuff salt of the formula are attached to the internal portion of the molecular r e SO a 5 consisting of chains and are frequently repeated along the molecular parts of the dyestuff salt chains, the improvement which comprises padding or 2 parts of the reaction product of 1 mol pprinting said materials with aqueous dispersions conhydroxydiphenyl with 1 mol benzyl chloride and 14 20 taining the salt of a basic dyestufi which is free from mol ethylene oxide carboxylic acid and sulfonic acid groups and a polynu- 2 parts of the condensation product of 2 mol clear aromatic sulfonic acid selected from the class naphthaIene-Z-sulphonic acid with l molformaldeconsisting of diphenyl sulfonic acid, naphthalene di-, hyde and tri-, or tetrasulphonic acid, and pyrene tetrasulfonic 56 parts of water are mixed with acid, and subsequently subjecting the thus treated ma- 80 parts of water at 50C and then with a solution of terials to a heat treatment. 1 part of the copper complex of the dyestuff of the 2. Process according to claim 1 wherein the salts of formula basic dyestuffs are of the anthraquinone series.

1 N '\T= CH5 I i I N N 00 H N 00 1i HO I 2 do Q H0 8 50 5 H0 S 5 HC CH -NI-I-CONI-I--CH=CH 2 parts of a sodium polyphosphate which yields a pH 3. Process according to claim 1 for the treatment of value f 5, 5 mixed textiles of cellulose and polyacrylonitrile con- 1 part of the reaction product of 1 mol oleyl alcohol taining anionic groups, wherein the mixed textiles are ith th l id d treated with aqueous dispersions of the salts obtained 10 parts di m l h t i 905 parts f water from basic dyestuffs which are free from carboxylic 100 P t f a ix d yam i ti f acid and sulphonic acid groups with polynuclear aro- 50 pans polyacrylonitrile d matic sulphonic acids, which also contain reactive dye- 50 parts f cotton 50 stuffs, and that the reactive dyestuffs are fixed in the are introduced into the resultant dyebath and the bath I P Y l f is heated with vivid circulation to 90C within 30 mihmess according to c aim 1 or the treatment of utes After dyeing at this temperature f 90 minutes mixed textiles of cellulose and polyacrylonitrile conthe bath is cooled to 40C and the fabric is rinsed with tainmg allionic groupsgwherfr'in the mixed textiles are a hot solution of 2 parts sodium alkylsulphate in 988 gzz gagi c digzt u s 31:51: 1 32 fgig zjfi lizfi gfig arts of water. p A differentiated red-yellow mixed yarn is obtained. If acid and sulphonic acid groups with polynuclear the dyestuff is used in the non-formulated form, precipmatif: sulnhqnic afjids and Subsequently, Without P itations occur and the cotton yarn is dyed with red dyeg' t ljf s tf g wlth Sohmons of Stuffi yes u s w 1c are me we Claim: 5. Process according to claim 1 wherein the salts of 1. In a process for dyeing anionically modified synbasic dyestuffs on the Series thetic material selected from the class consisting of t of Claim 4 Whefem th dyelngs are fixed by s earning.

polyacrylonitrile containing internal anionic groups, polyamide containing internal anionic groups, polyes- 6S Process of Clalm 4 wherem the dyemgs are fixed by ters containing internal anionic groups, and mixtures of the cold bath g UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3300383 DATED August 19 19 75 |NVENT0R(S) Dietrich Hildebrand et a].

It is certified that error appears in the ab0ve-identified patent and that said Letters Patent are hereby corrected as shown below:

Claim 7, change "bath" to ---batch-.

Signed and Scaled this Sixth Day of December I 977 [SEAL] Attest:

RUTH C. MASON LUTRELLE F. PARKER Attesting Ojficer Acting Commissioner of Patents and Trademarks 

1. IN A PROCESS FOR DYEING ANIONICALLY MODIFIED SYNTHETIC MATERIAL SELECTED FROM THE CLASS CONSISTING OF POLYACRYLONITRILE CONTAINING INTERNAL ANIONIC GROUPS, POLYAMIDE CONTAINING INTERNAL ANIONIC GROUP, POLYESTERRS CONTAINING INTERNAL ANIONIC GROUPS, AND MIXTURES OF SAID MATERIALS WITH OTHER FIBER MATERIALS, WHEREIN THE INTERNAL ANIONIC GROUPS ARE STRONG ANIONIC GROUPS THAT ARE ATTACHED TO THE INTERNAL PORTION OF THE MOLECULAR CHAINS AND ARE FREQENTLY REPEATED ALONG THE MOLECULAR CHAINS, THE IMPROVEMENT WHICH COMPRISES PADDING OR PRINTING SAID MATERIALS WITH AQUEOUS DISPERSIONS CONTAINING THE SALT OF A BASIC DYESTUFF WHICH IS FREE FROM CARBOXYLIC ACLID AND SULFONIC ACID GROUPS AND A POLYNUCLEAR AROMATIC SULFONATIC ACID SELECTED FROM THE CLASS CONSINTING OF DIPHENYL SULONIC ACID, NAPHALENS DI-, TRI-, OR TETRASULPHONIC ACID, AND PRENE TWETRASULFONIC ACID, AND SUBSEQUENTLY SUBJECTING THE THUS TREATED MATERIALS TO A HEAT TREATMENT.
 2. Process according to claim 1 wherein the salts of basic dyestuffs are of the anthraquinone series.
 3. Process according to claim 1 for the treatment of mixed textiles of cellulose and polyacrylonitrile containing anionic groups, wherein the mixed textiles are treated with aqueous dispersions of the salts obtained from basic dyestuffs which are free from carboxylic acid and sulphonic acid groups with polynuclear aromatic sulphonic acids, which also contain reactive dyestuffs, and that the reactive dyestuffs are fixed in the usual way.
 4. Process according to claim 1 for the treatment of mixed textiles of cellulose and polyacrylonitrile containing anionic groups, wherein the mixed textiles are treated with aqueous dispersions of the salts obtained from basic dyestuffs which are free from carboxylic acid and sulphonic acid groups with polynuclear aromatic sulphonic acids and subsequently, without intermediate rinsing, impregnated with solutions of direct dyestuffs which are fixed.
 5. Process according to claim 1 wherein the salts of basic dyestuffs are on the azo series.
 6. Process of claim 4 wherein the dyeings are fixed by steaming.
 7. Process of claim 4 wherein the dyeings are fixed by the cold bath method. 